Silicon dioxide dispersion

ABSTRACT

Stable, aqueous dispersion containing silicon dioxide powder having a hydroxyl group density of 2.5 to 4.7 OH/nm 2 , which is obtained from a silicon dioxide powder produced by a flame hydrolysis process under acid conditions. The dispersion is produced by incorporating the silicon dioxide powder into an aqueous solution by means of a dispersing device. The dispersion can be used to produce glass articles.

The invention concerns silicon dioxide dispersions, their production anduse.

Aqueous silicon dioxide dispersions are used in polishing applications(CMP), in the paper sector (inkjet) or in glass production.

For economic and applicational reasons, the use of dispersions having ahigh content of silicon dioxide powder is desirable here. Economic canrefer for example to the reduction of costs by transporting more highlyfilled dispersions. Such a dispersion can then be diluted to the desiredcontent on site.

Furthermore, special applications demand highly filled dispersions. Thisapplies for example to the production of glass articles. An aqueoussilicon dioxide dispersion can be converted first of all into a greenbody which by means of further heat treatment, optionally withsubsequent sintering, is converted into a glass body. The use of ahighly filled dispersion reduces shrinkage during production of thegreen body and minimises cracking.

It is known from U.S. Pat. No. 4,042,361 that aqueous dispersionscontaining silicon dioxide produced by a flame hydrolysis process and nostabilisers display an acceptable stability only up to a fill content ofup to 30 wt. %. With higher fill contents gelation or sedimentation canoccur within a very short time.

U.S. Pat. No. 5,116,535 describes a process for producing a stable,aqueous dispersion containing at least 35 wt. % of silicon dioxideproduced by a flame hydrolysis process and likewise no stabilisers. Inthis process silicon dioxide is introduced into water in a quantity thatinitially leads to a higher concentration in the dispersion than isdesired. In a second step this predispersion is diluted with water tothe desired concentration. The higher fill content achieved incomparison to U.S. Pat. No. 4,042,361 results from the higher viscosityof the predispersion, which increases the efficiency of dispersion. Thedisadvantage is that production of the dispersion involves two steps,and because of the high viscosity of the predispersion high dispersionenergies are necessary.

U.S. Pat. No. 5,246,624 describes the production of a stabiliseddispersion wherein silicon dioxide is introduced into acidified water ina concentration that is higher than desired. Acidification is preferablyperformed with mineral acids. The subsequent addition of base leads to astabilisation of the dispersions in the alkaline pH range and thedispersion can be diluted to the desired concentration.

The disadvantage here is that production has to be started in the acidrange. During the subsequent addition of base, the neutralisation causessalts to form, which can cause a disadvantageous change in therheological properties of the dispersion.

The object of the invention is to provide a silicon dioxide powder thatcan be incorporated into aqueous dispersions with high fill contents.The object of the invention is further to provide a dispersioncontaining this silicon dioxide powder which can be used as analternative to dispersions containing silicon dioxide obtained fromflame hydrolysis processes, without displaying their disadvantages.

The invention provides silicon dioxide powder that is characterised inthat it is a silicon dioxide powder produced by flame hydrolysis anddisplaying a hydroxyl group density of 2.5 to 4.7 OH/nm².

It is produced by treating silicon dioxide powder produced by flamehydrolysis under acid conditions.

Flame hydrolysis according to the invention refers to the formation ofsilicon dioxide by flame hydrolysis of at least one evaporable,silicon-containing compound in the gas phase of a flame. The flame isgenerated by the reaction of a hydrogen-containing fuel gas and anoxygen-containing gas. During this reaction water is formed in the formof water vapour, which leads to a hydrolysis of the silicon-containingcompound with formation of silicon dioxide. As is explained by J.Mathias and G. Wannemacher, Journal of Colloid and Interface Science 125(1988), the surface of the untreated silicon dioxide powder produced byflame hydrolysis displays a hydroxyl group density of approx. 1.8 to 2.5OH/nm². Even if additional water vapour is charged into the process, asdescribed for example in DE-A-1150955, the hydroxyl group densityremains within this range.

During flame hydrolysis highly disperse, non-porous primary particlesare initially formed which, as the reaction continues, can coalesce toform aggregates, and these can congregate further to form agglomerates.

Suitable silicon-containing compounds are for example silicontetrachloride, methyl trichlorosilane, ethyl trichlorosilane, propyltrichlorosilane, dimethyl dichlorosilane and mixtures thereof. Silicontetrachloride is particularly preferred. Suitable fuel gases arehydrogen, methane, ethane, propane, with hydrogen being particularlypreferred. The preferred oxygen-containing gas is air.

It is known from U.S. Pat. No. 5,256,386 that silicon dioxide particlesproduced by means of the sol-gel method, which are highly porous,spherical and non-aggregated, can be treated with acids to increase thehydroxyl group density.

The increase in the hydroxyl group density of a silicon dioxide powderproduced by flame hydrolysis, which takes the form of aggregates ofnon-porous primary particles, achieved by treatment under acidconditions is surprising.

An increased formation of agglomerates of silicon dioxide with loss offine-particle structures would have been expected. The consequence ofsuch structural changes would be that a powder treated in this way wouldno longer be suitable for many applications.

The person skilled in the art would not have considered a treatmentunder acid conditions as a means of increasing the hydroxyl groupdensity of a silicon dioxide powder produced by flame hydrolysis, sinceit is known that in a flame hydrolysis process water vapour is presentat many points and yet the powder obtained from the process onlydisplays a hydroxyl group density of less than 2.5 OH/nm².

The silicon dioxide powder according to the invention can beincorporated into aqueous media substantially faster than untreatedsilicon dioxide powder produced by flame hydrolysis.

Silicon dioxide powders produced by flame hydrolysis also include suchpowders that in addition to the silicon dioxide display a dopingcomponent. The production of such powders is described in DE-A-19650500.Typical doping components are for example aluminium, potassium, sodiumor lithium. The content of doping component should be no more than 1 wt.%.

Silicon dioxide powders produced by flame hydrolysis also additionallyinclude silicon-metal mixed oxide powders produced by flame hydrolysis,wherein the content of silicon dioxide is at least 60%.

In a preferred embodiment the hydroxyl group density of the silicondioxide powder can be between 3 and 4 OH/nm². The BET surface area ofthe silicon dioxide powder can be between 5 and 600 m²/g. It canpreferably be between 20 and 200 m²/g.

The invention also provides a process for producing the silicon dioxidepowder according to the invention, which is characterised in that asilicon dioxide powder produced by a flame hydrolysis process and havinga hydroxyl group density of less than 2.5 OH/nm² is treated attemperatures of 40 to 700° C. under acid conditions and for reactiontimes of 5 minutes to 20 hours and is subsequently separated from thereaction mixture.

Acid conditions refer to aqueous acids. Inorganic mineral acids such ase.g. hydrochloric acid, sulfuric acid or water-miscible carboxylic acidscan be used in particular.

The treatment can preferably be performed with aqueous hydrochloricacid. An embodiment can likewise be preferred wherein the acid residues,generally hydrochloric acid, from the production process adhere to thesilicon dioxide powder produced by flame hydrolysis.

The reaction times vary with the reaction temperature and with thenature and quantity of the acid involved in the reaction.

The silicon dioxide powder according to the invention can be obtaineddirectly in a step following on from the process. A step following onfrom the process refers to processing stages following thedeacidification stage. A simplified flow diagram of the known process isreproduced for example in Ullmann's Encyclopedia of IndustrialChemistry, Vol. A23, page 636, 5^(th) edition.

The invention also provides an aqueous dispersion containing the silicondioxide powder according to the invention.

An embodiment wherein the dispersion according to the invention does notthicken and forms no sediment for a period of at least 6 months can bepreferred.

The content of silicon dioxide in the dispersion according to theinvention can vary over broad ranges. Dispersions according to theinvention can be obtained with a content of 10 to 70 wt. %. The rangebetween 20 and 60 wt. % is preferred, the range between 30 and 50 wt. %being particularly preferred.

The pH of the dispersion according to the invention can be in a rangebetween 3 and 12. In the acid environment ranges between 3 and 6 arepreferred, the range between 4 and 5 being particularly preferred. Inthe alkali environment the ranges between 8.5 and 12 are preferred, therange between 9 and 10.5 being particularly preferred.

The pH of the dispersion can be adjusted using acids or bases ifnecessary. Both inorganic and organic acids can be used as acids.Examples of inorganic acids are hydrochloric acid, nitric acid orsulfuric acid. Examples of organic acids are carboxylic acids having thegeneral formula C_(n)H_(2n+1)CO₂H, where n=0-6, dicarboxylic acidshaving the general formula HO₂C(CH₂)_(n)CO₂H, where n=0-4, orhydroxycarboxylic acids having the general formula R₁R₂C(OH)CO₂H, whereR₁═H, R₂═CH₃, CH₂CO₂H, CH(OH)CO₂H or glycolic acid, pyruvic acid,salicylic acid or mixtures of the cited acids. Particularly preferredorganic acids can be acetic acid, citric acid and salicylic acid.

Alkali hydroxides, amines or ammonia can be used to raise the pH.Ammonium hydroxide, potassium hydroxide and tetramethyl ammoniumhydroxide can be particularly preferred.

Irrespective thereof, acids or bases can be added to the dispersionaccording to the invention to establish a desired pH.

The average aggregate diameter of the silicon dioxide powder in thedispersion according to the invention can be less than 200 nm andparticularly preferably less than 100 nm. The average aggregate diameterin the dispersion can be determined by dynamic light scattering.Dispersions with such fine-particle silicon dioxide can be used forpolishing surfaces.

The dispersion according to the invention can also contain oxidisingagent. The content of oxidising agent can be between 0.3 and 20 wt. %,relative to the dispersion. Typical oxidising agents can be hydrogenperoxide, hydrogen peroxide adducts or organic per-acids.

The dispersion according to the invention can also contain corrosioninhibitors. The content of corrosion inhibitors can be 0.001 to 2 wt. %,relative to the dispersion. Suitable examples of corrosion inhibitorscan be benzotriazole, substituted benzimidazoles, substituted pyrazines,substituted pyrazoles and mixtures thereof.

Surface-active substances, which can be of a non-ionic, cationic,anionic or amphoteric nature, can be added to further stabilise thedispersion according to the invention, for example againstsedimentation, flocculation and decomposition of additives. The contentof surface-active substances can be 0.001 to 10 wt. %, relative to thedispersion.

The invention also provides a process for producing the dispersionaccording to the invention which is characterised in that a silicondioxide powder produced by flame hydrolysis and having a hydroxyl groupdensity of 2.5 to 4.7 OH/nm² is incorporated into an aqueous solution bymeans of a dispersing device.

High-speed mixers, a toothed disc, rotor-stator machines, ball mills orattrition mills, for example, are suitable for incorporating the silicondioxide powder. Higher energy inputs are possible with a planetarykneader/mixer. The efficiency of this system depends on a sufficientlyhigh viscosity of the mixture to be processed, however, in order for thehigh shear energies needed to break down the particles to be introduced.Aqueous dispersions having average aggregate sizes of below 0.1 μm canbe obtained with high-pressure homogenisers.

In these devices two predispersed streams of suspension under highpressure are decompressed through a nozzle. The two jets of dispersionhit each other exactly and the particles grind themselves.

In another embodiment the predispersion can again be placed under highpressure, but the particles collide against armored sections of wall.The operation can be repeated any number of times to obtain smallerparticle sizes.

The invention also provides the use of the dispersion according to theinvention for the production of transparent coatings, for chemicalmechanical polishing, for glass production, for the production ofsol-gel glass articles, for example overcladdings, crucibles,accessories, coatings, sintered materials, inkjet papers.

EXAMPLES Analytical Chemistry

The BET surface area of the particles is determined according to DIN66131.

The hydroxyl group density is determined by the method published by J.Mathias and G. Wannemacher in Journal of Colloid and Interface Science125 (1988) by reaction with lithium aluminium hydride.

The viscosity is determined with a Brookfield viscometer at 23 degreesC.

The loss on drying (LOD) is determined at 105° C./2 hours by referenceto DIN/ISO 787/II, ASTM D 280, JIS K 5101/21.

Production of Silicon Dioxide Powders (P) Example PA1

700 g silicon dioxide powder (OX 50, Degussa) are refluxed in 2100 gwater and 2100 g hydrochloric acid (37%) for 18 h. The powder is thenremoved from the product by filtration and washed with water until a pHof 5 is obtained.

Example PA2

Performed in the same way as Example PA1 but without hydrochloric acid.

Example PB1

Performed in the same way as Example PA1 but with Aerosil 90 (DegussaAG) instead of OX 50.

Example PB2

Performed in the same way as Example PB1 but without hydrochloric acid.

Example PC1

Performed in the same way as Example PA1 but with Aerosil 200 (DegussaAG) instead of OX 50.

Example PC2

Performed in the same way as Example PC1 but without hydrochloric acid.

Example PD1

K-doped SiO₂ powder, produced according to DE-A-19650500, with watervapour being introduced after the deacidification zone.

Example PE1

Performed in the same way as Example PD1 but with Na-doped SiO₂ powderproduced according to DE-A-19650500.

Example PF1

Performed in the same way as Example PD1 but with Li-doped SiO₂ powderproduced according to DE-A-19650500.

Comparative materials bear the index 0 and are untreated samples. Theanalytical data for the treated and untreated silicon dioxide powders isreproduced in the table. The table shows that the treatment according tothe invention of silicon dioxide produced by a flame hydrolysis processunder acid conditions results in a markedly increased hydroxyl groupdensity, whilst the BET surface area of the treated and untreatedpowders remains unchanged within the limits of determination accuracy.Further evidence that the treatment according to the invention causes nosubstantial changes in the structure of the powder is provided by thetransmission electron micrographs in FIGS. 1A and 1B.

FIG. 1A shows the powder according to the invention from Example PA1,FIG. 1B shows the untreated powder from Example PA0.

TABLE Analytical data for silicon dioxide powders Starting ReactionTemperature BET OH density LOD Example material Treatment time [h] [°C.] [m²/g] [OH/nm²] [wt. %] PA0 OX 50 None — — 40 2.3 0.6 PA1 OX 50HCl/H₂O 18 100 40 4.6 0.51 PA2 OX 50 H₂O 18 100 41 4.7 0.58 PB0 AE 90None — — 84 2.4 0.8 PB1 AE 90 HCl/H₂O 18 100 80 4.7 1 PB2 AE 90 H₂O 18100 85 5.4 0.9 PC0 AE 200 None — — 198 2.1 0.9 PC1 AE 200 HCl/H₂O 18 100197 3.7 0.8 PC2 AE 200 H₂O 18 100 200 3.8 2.2 PD0 K/SiO₂ ⁽¹⁾ None — —132 1.8 0.5 PD1 K/SiO₂ Steam   0.1 550 130 2.8 0.7 PE0 Na/SiO₂ None — —89 1.9 0.6 PE1 Na/SiO₂ Steam   0.1 550 90 2.6 0.6 PF0 Li/SiO₂ None — —88 2.1 0.5 PF1 Li/SiO₂ Steam   0.1 550 91 2.7 0.6 ⁽¹⁾All doped powderswith 0.2 wt. % doping component

Production of Dispersions (D) Example D1

56 g of the powder from Example PA1 are stirred into 44 g water using anUltra-Turrax. A fill content of 56 wt. % is obtained. After 4 days aviscosity of 110 mPas is achieved with a shear rate of 10 rpm. Thedispersion is unchanged after a storage period of 6 months at roomtemperature.

Example D2 (Comparative Example)

Using the same dispersing device as in Example D1, a maximum of 30 wt. %of the powder from Example PA0 can be stirred in. The dispersionthickens further and becomes solid after approx. 4 weeks. The viscositymeasured after four days was 500 mPas at a shear rate of 10 rpm.

Example D3

Same as Example D1 but with the powder from Example PC1 instead of PA1.The result is a fill content of 28 wt. %, the viscosity was 140 mPas ata shear rate of 10 rpm.

Example D4 (Comparative Example)

Same as Example D1 but with powder from Example PC0. The result is amaximum fill content of 15 wt. % and a viscosity of 350 mPas at a shearrate of 10 rpm.

Example D5

56 g of the powder from Example PA1 are incorporated into 44 g waterusing an Ultra-Turrax. The pH is then adjusted to 10.5 with 1N KOH. Afill content of 53 wt. % is obtained.

Example D6

20 kg of powder PB1 are absorbed into 20 kg of demineralised water withthe aid of a dispersing and suction mixer from Ystrahl (at 4500 rpm) androughly predispersed. Following introduction of the powder, dispersionis completed at a speed of 11,500 rpm. The dispersion thus obtained isground with a high-pressure homogeniser, Ultimaizer system from SuginoMachine Ltd., model HJP-25050, at a pressure of 250 MPa and with adiamond die diameter of 0.3 mm and two grinding cycles. A fill contentof 50 wt. % is obtained. The average particle diameter (number related)determined with a Zetasizer 3000 Hsa from Malvern is 92 nm.

Dispersions D1, D3 and D5 and D6 display no sediment within 6 months.

1. An aqueous dispersion comprising a silicon dioxide powder dispersedin water, wherein the silicon dioxide powder is produced by flamehydrolysis and displays a hydroxyl group density of 2.5 to 4.7 OH/nm²,wherein the hydroxyl group density is determined by reaction of thesilicon dioxide powder with lithium aluminium hydride according to themethod of J. Mathias and G. Wannemacher in the Journal of Colloid andInterface Science 125 (1988).
 2. The aqueous dispersion according toclaim 1, wherein the dispersion, over a period of 6 months, does notthicken further and forms no sediment.
 3. The aqueous dispersionaccording to claim 1, wherein the dispersion has a content of silicondioxide powder between 10 and 70 wt. %.
 4. The aqueous dispersionaccording to claim 1, wherein the dispersion has a pH between 3 and 12.5. The aqueous dispersion according to claim 1, wherein the averageaggregate diameter in the dispersion is less than 200 nm.
 6. The aqueousdispersion according to claim 1, wherein the dispersion containsoxidising agents, corrosion inhibitors and/or surface-active substances.7. A method of making an aqueous dispersion the method comprisingincorporating a silicon dioxide powder into an aqueous solution by meansof a dispersing device; and producing the dispersion of claim
 1. 8. Amethod of using an aqueous dispersion, the method comprising applyingthe dispersion of claim 1 to a substrate.
 9. The aqueous dispersion ofclaim 4, wherein the pH of the aqueous dispersion is from 3 to
 6. 10.The aqueous dispersion of claim 4, wherein the pH of the aqueousdispersion is from 4 to
 5. 11. The aqueous dispersion of claim 4,wherein the pH of the aqueous dispersion is from 8.5 to
 12. 12. Theaqueous dispersion of claim 4, wherein the pH of the aqueous dispersionis from 9 to 10.5.
 13. The aqueous dispersion of claim 3, wherein theaqueous dispersion has a content of silicon dioxide powder of from 20 to60 wt. %.
 14. The aqueous dispersion of claim 3, wherein the aqueousdispersion has a content of silicon dioxide powder of from 30 to 50 wt.%.
 15. The aqueous dispersion of claim 1, further comprising a corrosioninhibitor.
 16. The aqueous dispersion of claim 15, wherein the corrosioninhibitor is comprised in the aqueous dispersion in an amount of from0.001 to 2 wt. %.
 17. The aqueous dispersion of claim 15, wherein thecorrosion inhibitor is selected from the group consisting of abenzotriazole, a substituted benzimidazole, a substituted pyrazine, asubstituted pyrazole, and combinations thereof.
 18. The aqueousdispersion of claim 1, further comprising an oxidising agent.
 19. Theaqueous dispersion of claim 18, wherein the oxidising agent is comprisedin the aqueous dispersion in an amount of from 0.3 and 20 wt. %.
 20. Theaqueous dispersion of claim 18, wherein the oxidising agent is selectedfrom the group consisting of hydrogen peroxide, a hydrogen peroxideadduct, an organic per acid, and combinations thereof.